Processes for the preparation of new carbohydrate compounds



M861! 9, 1954 K. M. GAVER :rm. 2.671.781

PROCESSES FOR THE PREPARATION OF NEW CARBOHYDRATE C Filed June 26, 1951 Moms 3 Sheets-Sheet 1 STAROH OR OTHER ALKALI HYOROXIDE m GLUOOPYRANOSE POLYMER NON-AQUEOUS SOLVENT I; I l ORGANIC REACTION TO PRODUCE Z-MONOALKALI HAUDE 'GLUCOPYRANOSE POLYMER H I 1, R X 7 l-locm 0H(0H-) (OHOH) lee-10M) 0.

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FIG. I

KENNETH M. GAVER INVHVTO S ATTORNEY Mild! 9, 1954 GAVER r 2.671,?81

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REACTION TO PRODUCE 2,3,6-TRIORGANIC GLUOPYRANOSE POLYMER Fl G 2 KENNETH M. GAVER DERK V. T|ESZEN ESTHER P. LASURE INVENTORS /Mlhu.

ATTORNEY Much 9, 1954 K. M GAVER EI'AL 2,671,781

PROCESSES FOR THE PREPARATION OF NEW CARBOHYDRATE COMPOUNDS Filed June 26. 1951 3 Shana-Sheet 3 STAROH OR OTHE R ALKALI HYDE OX IDE \N GLUGOPYRANOSE POLYMER NON AQUEOUS SOLVENT ORGA \c REACTION TO PRODUCE z-nonoALxAu mug: GLUOPYRANOSE POLYMER METALLIC 1 I O I SALT R noon, on (on-) (anon) (on on) (:18,

L l L I REAOTlON TO PRODUCE Z-MONOMETALLIO GLUOPYRANOSE POLYMER I o noon, on(on-) (ono-nnonon) c;

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r o noon,cn (on-i (cnonuononfiog AN'ON ETHERIFIGATlON, E-TO.

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IN VEN TORS no.3 "M 91% ATTORNEY Patented Mar. 9, 1954 PROCESSES FOR THE PREPARATION OF NEW OABBOHYDBATECOMPOUNDS Kenneth M. Gaver, Columbus, Ohio, Derk V. Tiessen, Delmar, N. Y., and Esther P. Lasure, Grove City, Ohio, assitnors to The Ohio State University Research Foundation, Columbus, Ohio, a corporation of Ohio Application June 26, 1851, Serial N0. 234,642

This application is in part a continuation of application Serial No. 694,326, filed August 31. 1946, now Patent 2,609,370, issued September 2, 1952.

The inventions disclosed in this application relate to new compositions of matter or compounds which we have prepared from glucopyranose polymer which have been heretofore unknown. The processes particularly described herein in illustration of our invention are especially designed to produce new products from starch.

In carrying out our process to produce preierred embodiments we produce as intermediate products certain new compounds which we have discovered and synthesized by our processes; these intermediate products when formed from starch being in the nature of alcoholates of starch. To designate these compounds. we have coined the word starchate" which we define as follows: Starchate" means and is used in this specification and in the claims hereof in the sense of a compound composed of an undetermined number of polymerized glucopyranose units wherein one or more metallic atoms or inorganic or organic radicals are substituted for the hydrogen atoms of one or more of the several hydroxyl groups or the starch unit so as to form a polymerized compound which in fact is (or is at least analogous to) an alcoholate of starch.

Prior to our inventions disclosed herein. a certain process had been discovered for the substitution of alkaline metals in the starch molecule to form a starchate which we will refer to hereinafter as the ammonia process and the ammonia proces starchate. As demonstrated in a patent application copending with parent application Serial No. 694.328. Serial No. 707,318 new issued as Patent No. 2,516,135 issued August 8.

1950, and as demonstrated hereafter in this ap-- plication, such prior art processes produce starchates which differ essentially from many of the starchates disclosed as intermediate products in this application. Also, in said Patent 2,518,135, there is disclosed the formation of a monosodium starchate and other monoalkali starchates and monometallic and monoorganic derivatives thereof, but as was demonstrated in said patent and as will be demonstrated hereafter herein such starchates also differ from the ammonia process starchates and from the polysubstituted starchates described herein.

Also, according to prior art methods. monoand polysubstituted products of cellulose and of simple sugars had been prepared, as for example, as

8 Claims. (CL 260-2333) 2 described in Scherer and Hussey. Journal of American Chemical Society. 53: 2344 (1931); Bchorigin et a1.. Berichte 69: 1713 (1936) Peterson and Barry, U. 8. Patent 2,157,083. 1939; un known British Patent 463,056 (1937) Muskat, Journal of American Chemical Society, 56: 693 (1934) and Muskat. Journal of American Chemical Society. 56: 2449 (1934). As will be demonstrated hereafter in this application. these sub-- stituted products of cellulose and of sugars are different from the products produced by our improved process. Referring again to the prior art processes designated above as the ammonia process." it may be noted that Schmid et a1. (Chemical Abstracts 20: 744 (1926) and Chen. Cent. 2: 1761 (1928) produced a monoalkall derivative of starch by treating the starch with an alkali metal in liquid ammonia. Either as a final product or as an intermediate product these investigators obtained a monoalkall compound in which it was concluded that the reaction occurred on the six position carbon in the glucose unit of the starch molecule. Other investigators obtained sodium hydroxide absorption compounds by dissolving starch in aqueous alkali followed by alcohol precipitation. These compounds, however, were not starchates in that the alkali metal did not enter into the starch molecule.

Likewise, if glycogen, inulin, etc. are treated in liquid ammonia with an alkali metal, a monoalkali derivative is formed which is similar to the ammonia process starchates referred to in the last paragraph. This monoalkali derivative differs essentially from the monoalkali derivative formed in the process described in Patent 2,510,135 in that the alkali metal in such ammonia process starchates is attached to the No. 6 carbon atom whereas the monoalkali starchate described in such patent and described herein in connection with many of the processes of our present inventions is one in which the alkali metal is attached to the No. 2 carbon atom.

Heretcfore, as stated above, it has been possible by known processes to form compounds in which metallic and nonmetallic elements. organic radicals, and/or other groups are substituted for one or more hydrogen atoms of one of the hydroxyl groups of a glucose or similar sugar. However, in the prior art processes dealing with starch it has not been possibl heretofore to accurately predetermine on which of the hydroxyl groups these substituted groups might be placed nor has it been possible to form compounds in which selected predetermined groups are substltuted on the various hydroxyl carbon atoms nortoiorm compounds whichhave one group eubstitutedononecarbonatomasecondcarbon atomandathirdgrouponathirdcarbonatom. We can, by our new p, iorm such compounds.

One of the objects of our invention is the provkion of new and useful products iormed irom starch.

Further objects and features of our invention will be apparent from a reading 01 the subjoined specification and claims when considered in connection with the accompanying drawings, showin: several exemplary illustrating certain ts or our inventions.

In the drawings:

Fig. l is a diagram illustrating a process forming monalkali starchates, monoorganic polyorsan c starchates and starchates having one or more organic radicals and also an alkali group substituted on the same glucopyranose unit, and oi forming similarly substitutcd poly rganic glucoses, glucosides, glucose derivatives, and glucoside derivatives;

Hg. 2 is a similar diagram illustrating alternative to form the same and similar products and also illustrating alternative steps by which monoorganic glucoses and glucosides and their derivatives; and nonalhali monometallic starchates and mixed organic and metallic starchates and derivatives thereof may also be formed; and

Pig. 8 is a similar diagram illustrating alternative ior producing the same and similar products.

In Patent 2,518,135 there are disclosed inventions relating to monometallic starchates (both alkali and nonalkali) to monoorganlc starchates. and to methods for their preparation. The claims oi! this application will be directed to the various mixed starchates produced by our improved processes. The invention disclosed in the aforesaid patent and its continuations are based upon the discovery that when starch is reacted with alcohol soluble hydroxides (such as the hydroxides of lithium, sodium. potassium, rubidium and caesium) under certain conditions there is produced a metallic starchate wherein the alkali metal is attached through an oxygen atom to a carbon atom in the complex-glucopyranose residue (the structure commonly considered as the building unit oi starch).

The starchate product iormed is a glucopyranose compound. The structural formula oi the unit forming the building unit 0! the complex starchate may be illustrated as tollows wherein W represents an alkali metal:

Investigation of the fl-monoalkali metal atarchate (when tested by titration and chemical reactions) definitely proves that the starch derivative formed is not an addition or coordinated but is a true alcohoiate of starch. This is further borne out in that the z-monoalkali, metal starchates (particularly the sodium or potassium starchates) produced have been found to be adapted as disclosed herein tor use as starting compounds in making other metallic derivatives. ethers, esters. and other typical compounds using nonaqueous reaction medium.

In preparing the i-monoalkali starchates relured to above, we have investigated the effect oi the following factors on the reaction.

/ Temperatures Any temperature irom C. up to 115 C. in an open or closed system, which permits the volatilization oi the water produced in the reaction produces z-monosodium starchate. It the system is closed so that the water evolved in the reaction is retained in the reaction mixture, then the reaction will yield 2-monosodium starchate at any reasonable temperature above 80 C., i. e., up to the dextrinization temperature (unknown in nonaqueous solvents but perhaps to 200 C. or higher). Somewhere above 115 C., in an open system, other reactions occur and the product is no longer ii-monosodium starchate. Under strongly dehydrating conditions. e. g. with alcoholates, this reaction can be driven to completion at temperatures lower than 80 C.

Pressure Apparently there is but very, very slight volume changes occurring in this reaction. Pressures up to 55 lbs. have been used with no eilect on the course oi the reaction or upon the product produced by the reaction. It is very probable that any practical pressure may be used provided the temperature and other requirements are not violated.

Time of reaction The time of reaction varies with the solvent chosen. With ethyl alcohol any time beyond two hours does not alter the course of the reaction nor the character oi the product. With butanol, the reaction is complete by the time the butanol (technical grade) reaches the boiling point of 115 C. A generalization may be made in that the reaction is completed within two hours at 80- 81' C. or instantaneously at 115 C. or higher regardless oi the nature of the solvent. Any temperature between 80 C. and 115 0. would require a proportionate reaction time (e. g. at C. the time required is about '15 min. and at C. the time required is about 15 min., etc.).

Alkali concentration It has been repeatedly demonstrated that the reaction is independent of alkali concentration and the same product is always obtained provided there is sufliclent alkali present to satisfy the requirements of the product. At the lower temperature range. i. e. 00 C., it is advisable to use an excess of alkali in order to complete the reaction in the two hour period. At the higher temperature range, 1. e. C. or higher only an amount of alkali approaching stoichiometric equivalent is necessary. The mother liquor from the latter reaction always shows a faint alkalinity approximating 0.04 N. This alkalinity apparently arises from the protein-alkali interaction product extracted from the starch. The protein is known to be extracted from the starch and appears in the mother liquor.

Nature of the alkali O! the alkalies onLv ammonia failed to react. Sodium and potassium hydroxide, sodium methylate, sodium ethylate, sodium propylate and sodium butylate all yield chemically similar products. Any caustic alkali or alkaline reacting material having an ionization constant of 2x10 or greater will react provided there is more than very slightly soluble in the chosen reaction media and also provided that the molecular size oi the reacting molecule is not too large to locate itself in position to react with the starch.

Similar reaction products were prepared using waxy rice, yucca, Base, arrowroot, sweet potato, potato, corn, wheat, tapioca and amioca starches; a series or thin boiling starches; wheat,potatc, tapioca and corn dextrins'; dextran: cotton; linen; sucrose; e-methyl glucoside; jute; ramie; cellulose: and inulin.

Mechanism of the reaction Water is evolved in the reaction and the amount of the water liberated is exactly chemically equivalent to the amount of alkali reacting with the starch to produce the Z-mono-alkali starchate. The proven overall reaction is (CsHmOs) +N8OH- (CsHsOsNi) +H2O The 2-alka1i metal starchates made with alkali metal hydroxides as described above, undergo the Williamson ether reaction to form derivative products. The following typical products have been produced by us and are illustrative.

(a) Ethyl starchate.

(b) Benzyl starchate.

(c) Isoamyl starchate.

(d) Butyl starchate.

(e) Hydroxyl ethyl starchate. (f) o-Chloro bennl starchate.

Thus, an alkali metal atom can be substituted on the No. 2 carbon of the basic starch unit by reacting or treating, in approximately stoichlometric quantities, starch (or similar natural or synthetic carbohydrates) with an alkali or alkaline reacting material (having an ionization constant of 2x10 or greater) in a solvent (containing enough of the alkali solution to produce 0.04 N or higher) at a temperature of 80 C. or higher (with or without agitation) for a period of two hours or longer. In such cases, a reaction will occur on the second carbon atom which will go practically to completion, provided alkali is present in sufllcient quantity to permit one mole of alkali to react with one mole (162 grams) oi starch. Under certain described exceptions, the temperature may be under 80 C. and under other described conditions the time may be under two hours.

Referring now to the diagrams of the drawlugs and especially to Fig. 1 for a detailed description of some of the processes illustrated, it may be seen that in the illustrated process, we react starch with an alkali hydroxide in a non-aqueous solvent as is fully described above. The alkali hydroxide may be sodium hydroxide, potassium hydroxide, rubidium hydroxide, caesium hydroxide or lithium hydroxide. Ammonia hydroxide is unsuitable. The nonaqueous solvent may be any solvent other than water which will dissolve sodium hydroxide to the extent of 0.04 N or higher. We have tested and found that the following solvents are all satisfactory and we have found no nonaqueous solvent which is unsatisfactory.

Solvents used It has been found that any of the following alcohols may be used to prepare monosodium starchate provided that certain other variables are sumciently controlled as will be discussed later. It must be understood that not all these mentioned have the same utility in the process. However, any solvent which will dissolve NaOH. even in small amounts, is a suitable vehicle in 6 which to carry out the reaction provided that certain other variables are sufliciently controlled.

Alcohols which may be used Allyl Iso-amyl n-amyl Sec.-amyl Tert.-amyl Anisyl Benzhydrol Benzoylcarbinol Benzyl 2,3-butanediol n-Butyl Iso-butyl Bec.-butyl Tert.-butyl Sec. butyl carbinol p (p-Tert. butyi phenoxy) ethyl Capryl Ceryl Cetyl 3-chloro-2-propenol-1 Cinnamic Crotyl Cyclohexanol Decyl Diacetone Diethyl carbinol Dimethyl benzyl carbinol Dlmethyl ethynyl carbinol Dimethyl n-propyi carbinol Dimethyl isopropyl carbinol Di-n-propyl carblnoi Di-iso-propyl carbinol Ethyl 2-ethyl butyl z-ethvl hexanol Furfuryl n-Heptyl n-Hexyl Sec.-hexyl Lauryl Methallyl Methyl Methyl amyl Methyl butyl carbinol o-Methyl cyclohexanol m-Methyl cyclohexanol p-Methyl cyclohexanol 2-methyl pentanol-l Methyl isopropyl carbinol n-Nonyl n-Octyl Octanol-it Pnenyl-propyl n-Propyl Iso-propyl Tetrahydrofurfuryl Triethyl carbinol 'Iriphenyl carbinol Various polyhydric alcohols which may also be used Ethylene glycol Ethylene glycol monomethyl ether Ethylene glycol monoethyl ether Ethylene glycol monobenzyl ether Ethylene glycol monobutyl ether Diethylene glycol Diethylene glycol monomethyl ether methylene glycol monoethyl ether Diethylene slycol monobenzyl ether methylene slycol mono tvl o r Di-propylene glycol Glycerol Glycerol s-n-butyl ether Glycerol ,a'-dimethyl ether Glycerol a,- -diphenyl ether Glycerol a-monomethyl ether Hexamethylene glycol 2-methyl-2,4-pentanediol Propylene glycol 'Irlethylene glycol Trimethylene glycol It is clear therefore that all nonaqueous solvents capable of dissolving the alkali to an extent comparable with the dissolving of sodium hydroxide to the extent oi 0.04 N or higher are satisfactory. Step one of the process illustrated in Fig. 1 thus produces a 2-monoalkali starchate having a formula:

Asasecondstepoftheprocessdisclosedin Fla. 1, we treat the il-monoalkali starchate formed by step 1 above with an etherifying agent. we may suspend the starchate in from i to 10 times the calculated quantity of an etherifylnl agent and heat (with pressure, if desired (to 80-81 C. forfromztoilihours. Bythisstepweobtaina z-monoorsanic starchate having a formula:

H HOCE1H(CH-) (CHOHKCBOR 11 (k- A dispersin: solvent may be used if desired but is unn. The reactants may be agitated or not, as desired. Pressure may be applied or not, as desired. The 2-monoalkal1 starchate may be treated in other manners with the organic compounds if desired. In the drawings. as examples we have designated these reactants as organic halides, but any organic compound containing a replaceable halogen or similarly reacting group is satisfactory. For instance, dimethyl sulfate, amyl nitrate. nitro paraflins, organic phosphates. acetates. benzoates. etc. are satisfactory. As further examples of the reactants which will react with the monoaikali metal or metallic starchate to produce the corresponding z-monoethers of such carbohydrates, the following may be mentioned:

sacid s-n-valeric acid a-hromo-iso-valeric acid n-Butyl bromide Iso-butyl bromide Sec.-hutyl bromide Tert.-butyl bromide n-Butyl chloride Iso-butyl chloride Sec-bum chloride 'lert.-butyl chloride n-Butyi chloroacetate Iso-butyl chlorocarbonate s-Butylene bromide p-Butylene bromide Iso-butylene bromide n-Butylidene chloride n-Butyl iodide Iso-butrl iodide Sec. butyl iodide Tert. butyl iodide Cetyl bromide Cetyl iodide Chloroacctamide Chloroacetodiethylamide Chloroacetic acid Chloroacetone Chloroacetonitrile Chlorobutane p-Chlorobutyric acid q-chlorobutyronitrile Chlorocyclohexane p-Chloroethyl acetate p-Chloromethyl chlorocarbonste Chloroform Chloropicrin a-Chloropropionic acid p-Chioropropionic acid p-Chloropropionitrile -Chloropropyl chlorocarbonate Decamethylene bromide s,p-Dibromobutyric acid 2,3-dibromopropene .B-Dibromopropionic acid p -Dibromopropyl alcohol 3,5-dibromopyridine .,o-Dibromosuccinic acid Dichloroacetic acid ww-Dichloropropyl ether p.s'-Dichloroiaopropyl ether Epibromohydrin Evichlorohydrin Ethyl bromide Ethyl bromoacetate Ethyl 'y-bromo-n-butyrate Ethyl e-bromo-n-caproate Ethyl bromomalonate Ethyl a-bromopropionate Ethyl p-bromopropionate Ethyl a-bromo-isovalerate Ethyl chloride Ethyl chloroacetate Ethyl u-chloroacetoacetate Ethyl chlorocarbonate Ethyl p-chloropropionate Ethyl dibromoacetate Ethyl dibromomalonate Ethyl dichloroacetate Ethylene bromohydrin Ethylene bromide Ethylene chloride II mime 9 Ethylene chlorohydrin Ethylidene bromide Ethylldene chloride Ethyl iodide Ethyl trichloroscetate Glycerol a.-y-dibromohydrin Glycerol a,-y-dichlorohydrin Glycerol .fi-dichlorohydrln Glycerol u-monochlorohydrin n-Heptyl bromide n-Heptyl iodide Hexechloroethane Hexcmethylene bromide n -Hexyl bromide n-Hexyl chiorocarbonate n-Hexyl iodide Iodoacetic acid Iodoiorm Lauryl bromide Lauryl chloride Methyl bromide Methyl bromoacetate Methyl p-bromopropionete Methyl chloroacetate Methyl chlorocarbonate Methyl chloroform Methyl u.p-dibromopropionate Methyl p-dichloropropionate Methylene bromide Methylene chloride Methylene iodide Myristyl bromide Methyl iodide n-Nonyl bromide n-Octadecyl bromide n-Octadecyl chloride Phenacyl bromide Phenacyl chloride n-Propyl bromide Isopronyl bromide n-Propyl chloride Isopropyl chloride Propylene bromide Propylene bromohydrin Propylene chloride Propylene chlorobromide Propylene chlorohydrin s-Tetrabromoethane s-Tetrachloroethane Tetrachloroethylene 1,1,2-tribromoethane Tribromoethylene 1,2.3-tribromo-2-methyl propane 1,2,3-tribromopropane Trichloroacetic acid 'Irlchloro-tert.-butyl alcohol 2,2,3 -trichlorobutyric acid 1,1,2-trichloroethane Trichloroethylene 1,2,3-trichloropropsne Triglycol dichloride Trimethylene bromide Trimethylene bromohydrin Trimethylene chloride Trimethylene chlorobromide Trimethylene chlorohydrin Triphcnylchloromethane o-Xylyl bromide m-Xylyl bromide p-xylyl bromide op-Xylylene bromide o-Xvlylene chloride ciellytheesters.

solvents may also be used:

Bec.-emyl benzene Tert.-smyl benzene Benzene n-Butyl benzene Sec.-butyl benzene Tert.-butyl benzene Cumene Cyclohexane 2.7-dimethyl octane Ethyl cyclohexsne Heptane Hexsne Hexsdecsne Ligroin Methyl cyclohexane Nonane n-Octane Isa-octane n-Pentane Petroleum ether Propyi benzene Tetrelsobutylene 'I'etredecane Toluene Tri-isobutylene Trimethyl butane Trimethylethylene 2,2,4-trimethyl pentene 'rriphenyl methane o-Xylene m-xylene p-xylene and various others.

The iollowing ketones may also be used:

Acetone Acetophenone Anlsolacetone Benzalacetone Benzophenone Benzoylacetone Diethyl Diisopropyl Ethyl phenyl Ethyl undecyi Methyl amyl Methyl butyl o-Methyl cyclohexanone m-Methyl cyclohexanone p-Methyl cyclohexanone Methyl ethyl Methyl hexyl Methyl n-propyl Methyl iso-nropyl and various others.

The i'ollowing ethers may also be used:

Ally] thyl n-Amyl Iso-amyl Anethole Anisole Benzyl Benzylmethyl n-Butyl benzyl n-Butyl n-Butyl phenyl 1,4-dioxane Dl-n-propyl 11 Benzyl ethyl Chloromethyl Dichloromethyl Diethylene glycol diethyl Ethyl butyl Ethylene glycol dibenzy Ethylene 8117 1 diethyl Ethyl Phenetoie n-Hexyl n-Propyl Iso-propyl and various others.

.By these various lists we do not mean to exclude the any other dispersing solvents.

As step three of the process shown in Fig. l, we react 2-monoorganic starchate resulting from step two with an alkali hydroxidein a nonaqueous solvent in the same manner as in step one with the difference that the temperature is raised to 115 C. or higher and provision is made for the removal of water. The same solvents as are used in step one are suitable: the same alkali hydroxides are suitable. The alkaline reacting material should have an ionization constant of 2 l0- or greater in a solvent containing enough of the alkali in solution to produce 0.04 N or higher at a temperature of 115 C. There may be a itation or not as desired. The reaction should continue for a period of one hour or longer. There must however be a provision for removal of water formed in the reaction. This is most im ortant and the provision for the removal of water together with the higher tem erature distinguish this step from the requirements of step one. It is essential as stated that the water evolved in the reaction be removed as rapidly as formed and therefore only those alcohols boiling at 115 C. or more have any utility as solvents in the reaction except in special cases where some other means have been devised to remove the water. At 115 C. the water is removed by boiling or distillation. At temperature below 115 C. special means must be provided for removing the water. This step of the process produces a 2- monoorganic, 3-monoalkall starchate, having a formula of I The fourth step of the illustrative process is similar to the second step. It comprises the reaction of the product of the third step with an organic reactant. This may be the same organic reactant as used in connection with the second step, or it may be a different organic reactant. It may be any one of the organic halides or similar reactants mentioned above in connection with step two. 0n treatment of the product, there is a reaction to produce a 2,3-diorganic starchate having a formula of In this step, as in the preceding step, the temperature should be kept at 115 C. or higher and precautions should be taken to prevent water contamination.

The fifth step of the illustrative process comprises the reaction of the product of the fourth step with an alkali metal dissolved in ammonia. As pointed out above, this process which comprises the fifth step is a step known in the prior steps of this process and the combination becomes a new process because it involves a new combination of steps, some of which are old and some of which are new.. Moreover, an entirely new product is obtained by this reaction. By it, we produce a 2,3-diorganic, d-monoalkali starchate having a formula of The sixth step of the illustrative process is similar to the second and fourth steps. In it we react the product of the fifth step with an organic reactant. This reactant may be thesame as used in step four, or may be entirely different from the reactant used in those steps. By this sixth step reaction, we produce a 2,3,6-triorganic starchate having a formula of So far we have described only one particular type of the processes disclosed herein. We will describe other types. We pause here, however, to ive some further idea of the number of new products which may be synthesized by our new processes. The following discussion in this paragraph refers only to the number of products which may be synthesized by processes following the type of the process described above as constituting steps one to eight of the process disclosed in Fig. 1. The number of reactants listed above as suitable for reaction in steps two, four and six include approximately eighty derivatives of chlorine. Thus we have at least eighty organic radicals (actually there are a great many more) which may be substituted either as R, It or R Inasmuch as any one of the radicals may be substituted for B, there are eighty difl'erent compounds which may be synthesized by the'first two steps. Inasmuch as any of the radicals may in each case be substituted as B" there are 1 or 8400 compounds which may be synthesized by the first four steps. Inasmuch as any of these radicals may be substituted as R there are 512,000 or (80) compounds which may be synthesized by the first six steps. Thus carrying the process through the sixth step enables us to produce approximately 500,000 new starchatcs.

The processes indicated in Fig. 2 parallel to some extent those described in connection with Fig. 1. However, the order of the steps of the processes disclosed in Fig. 2 are different from the order of the steps disclosed in Fig. 1, so that some new and different products are obtained. Also, several other branch processes are disclosed. Thus, while some of the products obtained by the processes disclosed in Fig. 2 are the same as the products obtained by the processes of Fig. 1, still there are disclosed new processes for producing the same new compounds as well as new processes for producing many other compounds not produced by the processes described in connection with Fig. 1. As in the process described in connection with Fig. l, the first step of the processes illustrated in Fig. 2 is the reaction of starch with an alkali hydroxide dissolved in a nonaqueous solvent to produce a 2-monoalkali starchate. This is exactly the same step as in the process described in Fig. 1. Moreover. the second step is also exactly the same and comprises the reaction of the 2-monoalkali starchate with an organic reactant to produce a 2-monoart. However, we combine it with the previous 7 organic starchate. From this product the main process indicated in Fig. 2 follows the line drawn down the center of the figure and comprises the reaction of the z-monoorganic starchate with an alkali metal dissolved in ammonia to produce a 2-monoorganic 3,6-dialkali starchate having a formula of H M'O CHaLH(OH-)(CHOM)(CHORD11 0- It will be noticed that this step three is similar to step five disclosed in Fig. 1. The result, however, is that the alkali metal is attached to both the No. 3 carbon atom and the No. 6 carbon with the result that the product of step three is entirely diil'erent from the product of either step three or step five of the previously described process. Step four is the reaction 01' this product with an organic reactant to produce a 2,3,6- triorganic starchate having a formula of O H B"OCH:(H(CH) (CHO R XCHO Rul O Although the designation of the organic radicals in the formula for this 2,3.6-triorganic starchate as shown in Fig. 2 diilers from that of the 2,3,B-triorganic starchate produced by the flrstsixstepsoftheprocessshowninFig. lasis disclosed by a comparison 01' the formula, yet the product may be exactly the same, depending upon the choice of the organic reactant for reaction in steps two,'four and six of the first process described, and for reaction in steps two and four of the processes described in connection with Fig. 2. Thus the products produced by this process may be produced by the process disclosed in Fig. 1, although the process diflers because of the different order of the steps. Moreover, because in the process described in connection with Fig. 1, different organic groups may be placed on carbon 3 and carbon 6 a greater number of different organic starchates may be synthesized thereby than by the process in connection with Fi 2.

We also disclose in connection with Fig. 2 processes for substituting nonalkali metallic groups in certain of the starchates. For example, we may react the 2-monoalkali starchate with a metallic salt to produce a 2-monometallic starchate, it being understood that in the formulas shown in the figures. while M is used to indicate an alkali metal, M alone is used to indicate a non-alkali metal. Such a 2-monometallic starchate may be represented by the formula of --o nocnicmcn-ncnomwnoml o Again the 2-monoorganic, 3,6-dialkali starchate produced by the third step of the main process disclosed in Fig. 2 may be reacted with a metallic salt to produce a z-monoorganic, 3.6- dimetallic starchate having a formula of O H MOCHsH(CH-)(CHOM)(GHOR L 0 Many of these metallic starchates may be further reacted to replace the anion groups of multiple valent derivatives.

The processes disclosed in Fig. 3 are similar in many respects to those disclosed in the first portion of Fig. 1. That is to say, the first five steps or the main process shown in Fig. 3 are exactly the same as the first five steps of the process disclosed in Fig. 1. This starch is reacted with an alkali hydroxide in a nonaqueous solvent to produce a z-monoalkali starchate. Thus 2-monoalkali starchate is converted by reaction with an organic compound to produce a 2-monoorganic starchate. This is reacted again with alkali hydroxide in a nonaqueous solvent at a higher temperature to produce a z-monoorganic, 3-monoalkali starchate. This is reacted with an organic compound to produce a 2,3-diorganic starchate. This is reacted with an alkali metal dissolved in ammonia to produce a 2,3-diorganic, G-monoalkali starchate having a formula of However, alternative processes disclosed in Fig. 3 are different from any of the processes previously disclosed in connection with Figs. 1 and 2. Thus, we show that the z-monoalkali starchate may be reacted with a metal salt to produce a 2- monometaliic starchate having a formula of The z-monoorganic, 3-monoalkali starchate may be reacted wit a metallic salt to produce a 2- monoorganic, 8-metallic starchate having a formula of O H HOCH1(H(CH-)(CHOM) (011011917 0- The 2,3-diorganic, fi-monoalkali starchate may be reacted with a metallic salt to produce a 2,3- diorganic, G-metallic starchate having a formula of [O H MOCHaCH(CH)(CHOR")(CHOR l o- Any one of the above described monometallic starchates may then be reacted to eflect replaceilllel'it of anion groups of multiple valent derivaves.

Above in connection with Figs. 2 and 3 we have described the replacement of alkali metals with non-alkali metals by reaction of the alkali starchates with metal salts. In each of the cases specified we can, if we wish, use a nonmetal inorganic salt as the reactant instead of a metal salt and obtain instead of the non-alkali metal starchates described in connection with said Figs. 2 and 3 corresponding non-metal inorganic starchates. Thus in fact we can react the alkali metal starchates with any salt, organic or inorganic, metal or non-metal and obtain corresponding organic or inorganic, metal or nonmetal starchates.

We have described in this application methods of synthesizing the following types of starchates and starchate derivatives in connection with the figures indicated:

Alkali starchates: Figures of drawings Figures of drawings Mixed organic non-alkali metal starchates:

As was demonstrated previously herein (assuming a list of only eighty organic radicals available for reaction 1. e. substitution as R, R", R R". and 3') it is clear that we have taught the synthesis of eighty z-monoorganic starchates: sixty-tour hundred 2,3-diorganic starchates; and live hundred twelve thousand. 2.3.6-triorganic starchates.

From the above it will be clear that it is impossible to give examples of the synthesizing all oi the products possible by our improved process or even to give examples of all oi the hundreds 0! products which we have actually synthesized.

Following are examples 0! the synthesis of various products by the use oi processes of our invention.

Inasmuch as certain steps of the procedures involved in many 0! the examples were identical or substantially identical. we set out now a series 01' directions or procedures which are iollowed in performing such steps. These directions or procedures are designated as Procedures I-V, inclusive, and in each oi the examples, we have merely .stated that certain of these procedures were employed. Thereby we have not only reduced the work of writing out the examples but have also. we believe, presented the examples in a manner by which they may be more readily understood. Following are the flve procedures referred to:

PROCEDURE I Preparation 0/ Z-sodium starchate In a 1000 ml. three-necked flask fitted with an eihcient agitator, a thermometer and a reflux condenser, place the i'ollowing:

100 grams of starch. 22 grams of sodium hydroxide. 500 ml. butanol.

Heat this mixture to 85 C. for 2 hours with vigorous agitation. Filter on suction. wash with butanol and then with toluene. The product. at this stage can be used directly in Procedure IV. The product may. however, be dried to produce 2- sodium starchate. The fl-sodium starchate must be protected from moisture and carbon dioxide during nitration, processing and drying. Drying can be best eflected in a vacuum at temperatures below 100' C. This procedure may be modified in certain ways, but the above is the procedure we recommend (or use with the other procedures i'ollowing.

PROCEDURE 11 Preparation of ZJ-disodium starchate (or 3-sodiam start-hate if 8-2 is occupied by an organic radical) iilogramsoistarch.

'iogramsoisodiumhydroxide.

'ifiomibutanol.

Slowly distil with vigorous agitation until the distillation temperature ceases to rise (or when the temperature reaches 118 0.). Filter hot with elaborate precautions to avoid contamination by moisture and wash twice with anhydrous butanol then with anhydrous toluene.

The product at this stage can be used directly in Procedure IV. The dry product is unstable.

It 0-2 is occupied by R then the amount of sodium hydroxide should be cut to 20 grams. This procedure may be modified relative to the alcohol. The mixture must boil in the range of 118 C. to 135 C. Other defined conditions are required.

PROCEDURE m Reaction of alkali on the Number 6 carbon of a a 2,3-dioraanic starchate In a 1000 m1. three-necked flask fitted with an eflicient agitator, an ammonia inlet and a stopper, and immersed 2 inches in a Dry Ice-acetone bath, place the following:

Pass dry ammonia gas into the flask until 500 ml. of liquid ammonia have been condensed. Introduce 25 grams of diorganlc starchate which soon disperses in the liquid ammonia under the influence oi agitation. Add sodium wire piecewise until the mixture turns a permanent blue. The excess sodium, indicated by the blue color, may be destroyed by small amounts of carbon dioxide.

PROCEDURE IV Etherification according to the reaction RONa+RD(-+RORI+NaX The sodium starchate prepared according to Procedures I or II is suspended in anhydrous toluene according to the following:

grams of starch (converted into the sodium starchate).

200 ml. toluene.

100 ml. of the organic halide.

This mixture is placed in a 1000 ml. bomb (preferably glass lined), sealed tight and autoclaved at 100 C. for about four hours.

The supernatant liquid is decanted (or filtered) oil! and the product repeatedly extracted hot with anhydrous butanol to remove the Na)! formed. This purified product is then washed with anhydrous toluene and then dried.

PROCEDURE V Etheriflcation according to the reaction ROH+R1X+NaOH-ROR+N9.X+H2O In a 1000 ml. three-necked flask fitted with an eflicient agitator, a thermometer and a reflux condenser. place the following:

100 grams of starch (converted into the derivative) 750 ml. 20% sodium hydroxide.

100 ml. organic halide.

Heat this mixture at 95 to C. for four hours with vigorous agitation. Neutralize the reaction mixture with HCl (1:1) and concentrate to a sirup under a vacuum. Take up the ether in alcohol and purity in the usual manner.

Example L-Sunthesis of Z-ethul, 3-n prowl, 6-1: butul starchate The following enumerated steps are used to preparethisstarchate:

1. Procedure I applied to produce z-sodium starchate.

2. Procedure IV applied with ethyl bromide to produce z-ethyi etarchate.

3. Procedure II applied to produce 2-ethyl, 3- sodium starchate.

4. Procedure IV applied with n-propyl bromide to produce 2-ethyl. 3-n propyl etarchate.

5. Procedure III applied to produce Z-ethyl. S-n propyl, 6-sodium starchate.

6. Procedure IV applied with n-butyl bromide to produce 2-ethyl, 3-n propyl, B-n butyl starchate.

Emmple II.-Snmthesie of 2-11 prowl, 3-hoproppl, d-benzpl etcrchct The following enumerated steps are used to prepare this starchate:

1. Procedure I applied to produce z-sodium starchate.

2. Procedure IV applied with n-propyl bromide to produce 2-n propyl starchate.

3. Procedure II applied to produce z-n propyl, S-sodium starchate.

4. Procedure IV applied with isopropyl bromide to produce 2-n propyl, S-isopropyl starchate.

5. Procedure V applied with benzyl chloride to produce2-npropyl,8-isopropyl,6-benzyl ltarchate.

Example HIP-Synthesis of Z-n prowl. J-methyl, d-leobutpl starchcte The following enumerated steps are used to Pr pare this starchate by a method consisting of a combination or steps diiIering irom or dinering in order from the steps or the method described in Example II:

1. Procedure I applied to produce z-sodium starcha 2. Procedure IV applied with n-propyl bromide to produce 2-n propyl bromide.

3. Procedure 11 applied to produce 2-n propyl, 3-eodium etarchate.

4. Procedure IV applied with methyl iodide to produce 2-n propyl, fl-methyl starchate.

5. Procedure III applied to produce 2-n propyl. ii-methyl, G-sodium starchate.

6. Procedure IV applied with isobutyl bromide to produce 2-n propyl. il-methyl. B-isobutlrl starchate.

Example Ive-Synthesis o! Z-methyl, S-ethyl star-chore The following enumerated steps are used to prepare this etarchate:

1. Procedure I applied to produce 2-eodium starchate.

2. Procedure IV applied with methyl iodide to produce 2-methyl starchate.

8. Procedure 11 applied to produce z-methyl. S-sodium starchate.

4. Procedure IV applied with ethyl bromide to produce S-methyl. S-ethyl etarchate.

Ecample ill-Synthesis of Z-ethyl, .l-methyl, 8- ieopropyl etcrchcte The following enumerated steps are used to prepurethiestarchate:

1. Prg'cedure I applied to produce a-sodium 2. Procedure IV applied with ethyl bromide to produce z-ethyl starchate.

3. Procedure II applied to produce fl-ethyl, 3- eodlinn ltarchate.

4. Procedure IV applied with methyl iodide to produce Z-ethyl, (l-methyl starchate.

5. Procedure III applied to produce Z-ethyl, 3- methyi, G-sodium starchate.

6. Procedure IV applied with isopropyl bromide to produce 2 ethyl, 3 methyl, 6 isopropyl starchate.

Example VL-Sunthesis of 2-methpl, 3-ethyl. d-beneul stcrchate The following enumerated steps are used to prepare this starchate:

1. Procedure I applied to produce 2-sodium starchate.

2. Procedure IV applied with methyl iodide to produce z-methyl starchate.

3. Procedure II applied to produce z-methyl, S-sodium starchate.

4. Procedure IV applied with ethyl bromide to produce Z-methyl, 3-ethyl starchate.

5. Procedure V applied with benzyl chloride to produce z-methyl, S-ethyl, B-benzyi starchate.

Example VIL-Sunthesis of Z-methul, .l-ethyl, (i-benzyl stcrchcte The following enumerated steps are used to prepare this starchate:

1. Procedure I applied to produce z-eodlum starchate.

2. Procedure IV applied with methyl iodide to produce 2-methyl starchate.

3. Procedure II applied to produce 2-methyl. 3-sodium starchate.

4. Procedure IV applied with ethyl bromide to produce Z-methyl. 3-ethyl starchate.

5. Procedure III applied to prepare 2-methyl, S-ethyl, d-sodium starchate.

6. Procedure IV applied with benzyl bromide to produce z-methyl, 3-ethyl, B-benzyl starchate.

Example VIIIr-SWWIS o! Z-methyl, .i-ethvl. d-butyl starchote The following enumerated stepe are used to prepare this starchate:

1. Procedure I applied to produce 2-sodium starchate.

2. Procedure IV applied with methyl iodide to produce 2-methyl starchate.

3. Procedure II applied to produce fl-methyl, B-sodium etarchate.

4. Procedure IV applied with ethyl bromide to produce 2-methyl, S-ethyl starchate.

ii. Procedure V applied with n-butyl bromide to produce 2-methyl, S-ethyl, d-n-butyl starch- 0 Example [IF-Sentinel: o1 Z-methyl, .l-etlwl. d-butul etarchate 19 Example X.Sunthesis o] Z-metlwl, .t-ethyl, d-butyl starchatc The following enumerated steps are used to prepare this starchate:

1. Procedure I applied to produce 2-sodium starchate.

2. Procedure IV applied with methyl iodide to produce 2-methyl starchate.

3. Procedure 11 applied to produce 2-methyl, S-sodium starchate.

4. Procedure IV applied with ethyl iodide to produce 2-methyl, S-ethyl starchate.

5. Procedure IlI applied to produce Z-methyl, 8-ethyl. B-sodium starchate.

6. Procedure IV applied with n-butyl bromide to produce z-methyl, 3-ethyl, d-n-butyl starchate.

Example XL-Synthesis of Z-metlwl, 3-ethvl, d-isopropul stcrchote When an alkali metal atom is substituted on carbon 2 and the alkali metal is replaced by an alkyl radical, the structure becomes where R represents the alkyl. Then when the 3 and 6 carbons are replaced by an alkali metal atoms, the structure becomes M OOH: H(CH)(CBOM )(OHOR) where M is an alkali metal atom.

If the alkali metal atoms on the 3 and 6 are replaced by either non metal cations. cations of metal salts other than salts of alkali metals and salts of ammonium or ethereal salts having a radical differing from the radical represented by R, the structure becomes where G represents any one of the above mentioned non metal cations. cations of metal salts other than salts of alkali metal and salts of ammonium and ethereal salts having a radical difiering from R.

If the polymer having an alkali metal atom on carbon 2 is mixed with alkali metal in liquid ammonia, further alkali metal becomes substi- 20 tuted on carbons 3 and 6 to form a polymer of which the unit structure becomes This polymer may be mixed with a metal salt to form a non-alkali metal trimetal polymer of which the unit structure becomes 6 O H MOCHrHUZH-MCHOMKOHOM) 11 0- where M represents a metal atom other than an alkali metal atom.

lm'ilhe Formulas 3, 4, 5 and 6 may be generalized where G represents either an alkali metal atom. a metal atom derived from a metal salt other than an alkali metal salt, or a cation derived from an ethereal salt and 6 represents either an alkali metal atom, a non-metal atom, a cation derived from an ethereal salt diifering from the cation represented by G or a cation derived from a metal salt other than an alkali metal salt provided that where G is an alkali metal atom or other metal cation. G must represent an identical metal cation.

As stated above, inventions relating to monometallic starchates (both alkali and non-alkali); monoorganic starchates: polyalkali starchates; polymetallic starchates (non-alkali); and methods for the preparation of all such starchates have or will be fully disclosed and claimed in copending applications.

It is to be understood that the described embodiments of our invention are only illustrative and are not intended to limit the invention. Especially is it to be understood that while we have used starch" and starchate throughout and have illustrated our invention by processes applied to starch, yet as is pointed out on column 5 above. the processes apply equally to other glucopyranose polymer. The scope of the invention is defined by the following claims.

We claim:

1. A method of making selectively, substantially uniformly substituted 2,3,6-trisubstituted glucopyranose polymer comprising reacting glucopyranose polymer with alkali metal hydroxide at a temperature in the range of approximately 78' C. to 98 C. in a nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 760 mm. pressure with the alkali metal hydroxide present in at least stoichiometric quantities relative to the glucopyranose polymer to produce a 2-monoalkali metal glucopyranose polymer; and reacting the 2-monoalkali metal glucopyranose polymer so formed in a nonaqueous system with an ethereal salt dissociatable at a temperature of approximately 78 C. to C. in a nonaqueous system to produce a 2-monoorganic glucopyranose polymer; reacting the Z-monoorganic glucopyranose polymer so formed by mixing it with a solution of an alkali metal dissolved in liquid ammonia with the alkali present in approximately double stoichiometric quantities to produce a 2-monoorganic-3.6-dialkali glucopyranose polymer; and reacting the monoorganic dialkali glucopyranose polymer so formed by mixing it in a nonaqueous system with salt dissociatable in a nonaqueous system and selected from the group consisting of ethereal salts, nonmetal salts, and metal salts other than salts of alkali metals and of ammonia. to produce a 2.3.6- trisubstituted glucopyranose polymer in which the substituents on the z-carbon of the glucopyranose units making up the glucopyranose polymer are substantially all identical with each other and are substantially uniformly cations selected from the group consisting of cations derived from ethereal salts and the substituents on the 3 and 6 carbons thereof are substantially all identical with each other and are substantially uniformly cations selected from the group consisting of cations derived from ethereal salts. nonmetal salts and metal salts other than salts of alkali metals and of ammonia.

2. A method of making selectively, substantially uniformly substituted 2,3.6-polysubstituted glucopyranose polymer comprising reacting glucopyranose polymer to replace one of the hydroxyl hydrogens thereof with an alkali metal atom by a reaction consisting of mixing glucopyranose polymer with alkali metal hydroxide at a temperature in the range of approximately 78 C. to 98 C. in a nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 760 mm. pressure with the alkali metal hydroxide present in at least stoichiometric quantitles in relation to the glucopyranose polymer to produce a 2-monoalkali metal glucopyranose polymer; and reacting the Z-monoalkali metal glucopyranose polymer so formed in a nonaqueous system with an ethereal salt dissociatable at a temperature of approximately 78 C. to 115 C. in a nonaqueous system to produce a 2-monoorganic glucopyranose polymer; reacting the 2- monoorganlc glucopyranose polymer so produced with a solution of alkali metal dissolved in liquid ammonia with the alkali present in approximately double stoichiometric quantities to produce a 2-monoorganic-3,6-dialkali glucopyranose polymer in which the substituents on the 2-carbon of the glucopyranose units making up the glucopyranose polymer are substantially all identical with each other and are substantially uniformly cations derived from ethereal salts, and the substituents on the 3 and 6 carbons thereof are substantially identical with each other and are substantially uniformly alkali metal atoms.

3. A method of making selectively, substantially uniformly substituted 2-monoorganic-3,6- dimetallic glucopyranose polymer comprising reacting glucopyranose polymer with alkali metal hydroxide at a temperature in the range of approximately 78" C. to 98 C. in a nonaqueous alcoholic system in which the alcohol boils at a temperature above 78'' C. at 760 mm. pressure with the alkali metal hydroxide present in at least stoichiometric quantities in relation to the glucopyranose polymer to produce a 2-monoalkali metal glucopyranose polymer; and reacting the 2-monoalkali metal glucopyranose polymer so formed in a nonaqueous system, with an ethereal salt dissociatable at a temperature of approximately 78 C. to 115 C. in a nonaqueous system to produce a 2-monoorganic glucopyranose polymer; reacting the 2-monoorganic glucopyranose polymer so produced by mixing it with a solution of an alkali metal dissolved in liquid ammonia with the alkali present in approximately stolchiometric quantities to produce a substantially uniformly substituted 2-monoorganlc-Ii,6-dialkali glucopyranose polymer; and reacting the 2-monoorganic-3,6-dialkali glucopyranose polymer so formed by mixing it in a nonaqueous system with a metal salt which is disiatable in a nonaqueous system and which is a metal salt other than salts of alkali metals and of ammonia. to produce a. 2,3,6-trisubstituted glucopyranose polymer in which the substituents on the 2-carbon of the glucopyranose units making up the glucopyranose polymer are substantially all identical with each other and are substantially uniformly cations derived from ethereal salts and the substituents on the 3 and 6 carbons thereof are substantially all identical with each other and are substantially uniformly metal atoms of metals other than alkali metals.

4. A method of making selectively, substantially uniformly substituted 2-monoorganic-3,6- dialkali starchate comprising reacting starch with alkali metal hydroxide at a temperature in the range of approximately 78' C. to 98 C. in a nonaqueous alcoholic system in which the alcohol boils at a temperature above 78' C. at 760 mm. pressure with the alkali metal hydroxide present in at least stoichiometric quantities in relation to the starch to produce a 2-monoalkali metal starchate; reacting the 2-monoalkali metal starchate so formed in a nona/queous system, with an ethereal salt dissoclatable at a temperature of approximately 78 C. to 115 C. in a nonaqueous system to produce a 2-monoorganlc starchate; reacting the 2-monoorganic starchate so produced by mixing it with a solution of an alkali metal dissolved in ammonia with the alkali present in approximately stoichiometric quantities to produce a 2-monoorganlc-3,6-dlalkli starchate in which the substituents on the 2-carbon of the glucopyranose units making up the starchate are substantially all identical with each other and are substantially uniformly cations derived from ethereal salts and the substituents on the 3 and 6 carbons thereof are substantially all identical with each other and are substantially uniformly alkali metal atoms.

5. A process of forming substantially uniformly substituted polysubstituted derivatives of glucopyranose polymer which comprises reacting glucopyranose polymer at a temperature of from C. to C. with alkali metal hydroxide in a substantially nonaqueous alcoholic system in which there is enough of the alkali to permit a mole of alkali to react with each glucopyranose polymer unit and to maintain an 0.04 N solution having an ionization constant of 2x10- or greater to produce a 2-monoalkali metal glucopyranose polymer; reacting the monoalkali metal glucopyranose polymer at a temperature of from 80' C. to 115 C. with an alkyl ester whereby alkyl radicals replace the alkali metal cations to produce a monosubstituted alkyl glucopyranose polymer; reacting the substituted monoalkyl glucopyranose polymer so formed by mixing it with a solution of alkali metal in liquid ammonia in which there is suflicient alkali metal to permit two moles of alkali to react with each mole of the substituted glucopyranose polymer to form a 2-alkyl, 3,6-alkali glucopyranose polymer; and replacing the alkali metal substituents on the 3, 6 carbons by mixing the 2-monoalkyl,3,6-dialkali metal glucopyranose polymer in a nonaqueous system at a temperature of from 80 C. to 115 C. with ethereal salt dissociatable at a temperature of approximately 80 C. to 115 C. in a nonaqueous system whereby the ethereal salt cations replace the alkali metal cations to produce by a double decomposition a polysubstituted 2-alkyl,3,6-substituted glucopyranose polymer in which the substituents on the 2-carbon of the glucopyranose units making up the gluco- Pym-nose polymer are substantially all identical with each other and are uniformly cations derived from ethereal salts and the substituents on the 3 and 6 carbons thereof are substantially all identical with each other and are uniformly cations derived from ethereal salts.

6. A new composition of matter consisting 01 a glucopyranose polymer composed of uniformly substituted 2,3,6-trimetallic gluoopyranoee units.

7. The method described in claim 1 in which the glucopyranose polymer originally reacted is a starch and the product is a substituted starchate.

8. The method described in claim 3 in which 24 the glucopyranose polymer Originally reacted is a starch and the product is a substituted starchate.

Number Name Date 2. 1 .1 Gaver Aug. 8, 1950 2,572,923 Gaver Oct. 30. 1951 

1. A METHOD OF MAKING SELECTIVELY, SUBSTANTIALLY UNIFORMLY SUBSTITUTED 2,3,6-TRISUBSTITUTED GLUCOPYRANOSE POLYMER COMPRISING REACTING GLUSOPYRANOSE POLYMER WITH ALKALI METAL HYDROXIDE AT A TEMPERATURE IN THE RANGE OF APPROXIMATELY 78* C. TO 98* C. IN A NONAQUEOUS ALCOHOLIC SYSTEM IN WHICH THE ALCOHOL BOILS AT A TEMPERATURE ABOVE 78* C. TO 760 MM. PRESSURE WITH THE ALKALI METAL HYDROXIDE PRESENT IN AT LEAST STOICHIOMETRIC QUANTITIES RELATIVE TO APGLUCOPYRANOSE POLYMER TO PRODUCE A 2-MONOALKALI METAL GLUCOPYRANOSE POLYMER; AND REACTING THE 2-MONOALKALI METAL GLUCOPYRANOSE POLYMER SO FORMED IN A NONAQUEOUS SYSTEM WITH AN ETHEREAL SALT DISSOCIATABLE AT A TEMPERATURE OF APPROXIMATELY 78* C. TO 115* C. IN A NONAQUEOUS SYSTEM TO PRODUCE A 2-MONOORGANIC GLUCOPYRANOSE POLYMER; REACTING THE 2-MONOORGANIC GLUCOPYRANOSE POLYMER SO FORMED BY MIXING IT WITH A SOLUTION OF AN ALKALI METAL DISSOLVED IN LIQUID AMMONIA WITH THE ALKALI PRESENT IN APPROXIMATELY DOUBLE STOICHIOMETRIC QUANTITIES TO PRODUCE A 2-MONOORGANIC-3,6-DIALKALI GLUCOPYRANOSE POLYMER; AND REACTING THE MONOORGANIC DIALKALI GLUCOPYRANOSE POLYMER SO FORMED BY MIXING IT IN A NONAQUEOUS SYSTEM WITH SALT DISSOCIATABLE IN A NONOAQUEOUS SYSTEM AND SELECTED FROM THE GROUP CONSISTING OF ETHERAL SALTS, NONMETAL SALTS, AND METAL SALTS OTHER THAN SALTS OF ALKALI METALS AND OF AMMONIA, TO PRODUCE A 2,3,6TRISUBSTITUTED GLUCOPYRANOSE POLYMER IN WHICH THE SUBSTITUENTS ON THE 2-CARBON OF THE GLUCOPYRANOSE UNITS MAKING UP THE GLUCOPYRANOSE POLYMER ARE SUBSTANTIALLY ALL IDENTICAL WITH EACH OTHER AND ARE SUBSTANTIALLY UNIFORMLY CATIONS SELECTED FROM THE GROUP CONSISTING OF CATIONS DE-RIVED FROM ETHEREAL SALTS AND THE SUBSTITUTENTS ON THE 3 AND 6 CARBONS THEREOF ARE SUBSTANTIALLY ALL IDENTICAL WITH EACH OTHER AND ARE SUBSTANTIALLY UNIFORMLY CATIONS SELECTED FROM THE GROUP CONSISTING OF CATIONS DERIVED FROM ETHEREAL SALTS, NONMENTAL SALTS AND METAL SALTS OTHER THAN SALTS OF ALKALI METALS AND OF AMMONIA. 